EP3763802B1 - Thiophenverbindung, flüssigkristallines medium und flüssigkristallanzeige damit - Google Patents

Thiophenverbindung, flüssigkristallines medium und flüssigkristallanzeige damit Download PDF

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EP3763802B1
EP3763802B1 EP19185360.5A EP19185360A EP3763802B1 EP 3763802 B1 EP3763802 B1 EP 3763802B1 EP 19185360 A EP19185360 A EP 19185360A EP 3763802 B1 EP3763802 B1 EP 3763802B1
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atoms
compounds
denotes
alkyl
fluorinated
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EP3763802A1 (de
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Atsutaka Manabe
Constanze Brocke
Sven Baran
Sebastian HOFMEYER
Alexander Hahn
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Merck Patent GmbH
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Merck Patent GmbH
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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3048—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon double bonds
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    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/123—Ph-Ph-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/124—Ph-Ph-Ph-Ph
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3004—Cy-Cy
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3009—Cy-Ph
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/301—Cy-Cy-Ph
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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3025—Cy-Ph-Ph-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring

Definitions

  • the present invention relates to novel compounds, novel liquid crystalline media, in particular for use in liquid crystal displays, and to these liquid-crystal displays, particularly to liquid-crystal displays which use the IPS ( i n- p lane switching) or, preferably, the FFS (fringe field switching) effect using dielectrically positive liquid crystals.
  • the last one is also called SB-FFS (super brighness FFS) effect occasionally.
  • dielectrically positive liquid crystals are used, which comprise one or more compounds having at the same time a high dielectric constant parallel to the molecular director and perpendicular to the molecular director, leading to a large average dielectric constant and a high dielectric ratio and, preferably, to a relatively small dielectric anisotropy at the same time.
  • the liquid crystalline media optionally additionally comprise dielectrically negative, dielectrically neutral compounds or both.
  • the liquid crystalline media are used in a homogeneous (i.e. planar) initial alignment.
  • the liquid-crystal media according to the invention have a positive dielectric anisotropy and comprise compounds having at the same time large dielectric constants parallel and perpendicular to the molecular director.
  • the media are distinguished by a particularly high transmission and reduced response time in respective displays, which is brought about by their unique combination of physical properties, especially by their dielectric properties and in particular by their high ratio of ( ⁇ / ⁇ av. ) respectively of the high values of their dielectric ratio ( ⁇ / ⁇ ). This also leads to their excellent performance in the displays according to the invention.
  • IPS and FFS displays using dielectrically positive liquid crystals are well known in the field and have been widely adopted for various types of displays like e.g. desk top monitors and TV sets, but also for mobile applications.
  • IPS and in particular FFS displays using dielectrically negative liquid crystals are widely adopted.
  • the latter ones are sometimes also called UB-FFS (ultra bright FFS).
  • UB-FFS ultra bright FFS
  • Such displays are disclosed e.g. in US 2013/0207038 A1 . These displays are characterized by a markedly increased transmission compared to the previously used IPS- and FFS displays, which have been dielectrically positive liquid crystals.
  • These displays using dielectrically negative liquid crystals have the severe disadvantage of requiring a higher operation voltage than the respective displays using dielectrically positive liquid crystals.
  • Liquid crystalline media used for UB-FFS have a dielectric anisotropy of -0.5 or less and preferably of -1.5 or less.
  • Liquid crystalline media used for HB-FFS have a dielectric anisotropy of 0.5 or more and preferably of 1.5 or more.
  • Respective media comprising both dielectrically negative and dielectrically positive liquid crystalline compounds, respectively mesogenic compounds are disclosed e.g. in US 2013/0207038 A1 . These media feature rather large values of ⁇ and of ⁇ av . already, however, their ratio of ( ⁇ / ⁇ ) is relatively small.
  • the IPS or the FFS effect with dielectrically positive liquid crystalline media in a homogeneous alignment are preferred.
  • LC phases which can be used industrially are required to have a liquid-crystalline mesophase in a suitable temperature range and low viscosity.
  • None of the series of compounds having a liquid-crystalline mesophase that have been disclosed hitherto includes a single compound which meets all these requirements. Mixtures of two to 25, preferably three to 18, compounds are therefore generally prepared in order to obtain substances which can be used as LC phases.
  • Matrix liquid-crystal displays are known.
  • Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors).
  • active matrix is then used, where in general use is made of thin-film transistors (TFTs), which are generally arranged on a glass plate as substrate.
  • TFTs comprising compound semiconductors, such as, for example, CdSe, or metal oxides like ZnO or TFTs based on polycrystalline and, inter alia, amorphous silicon.
  • CdSe compound semiconductors
  • metal oxides like ZnO metal oxides like ZnO
  • TFTs based on polycrystalline and, inter alia, amorphous silicon The latter technology currently has the greatest commercial importance worldwide.
  • the TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counter electrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image.
  • This technology can also be extended to fully colour-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is located opposite each switchable pixel.
  • the TFT displays most used hitherto usually operate with crossed polarisers in transmission and are backlit.
  • ECB (or VAN) cells or FFS cells are used, whereas monitors usually use IPS cells or TN (twisted nematic) cells, and notebooks, laptops and mobile applications usually use TN, VA or FFS cells.
  • MLC displays of this type are particularly suitable for TV applications, monitors and notebooks or for displays with a high information density, for example in automobile manufacture or aircraft construction.
  • problems regarding the angle dependence of the contrast and the response times difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [ TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp.
  • VAN v ertically aligned nematic
  • IPS displays for example: Yeo, S.D., Paper 15.3: "An LC Display for the TV Application", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 758 and 759
  • TN displays as one of the three more recent types of liquid-crystal display that are currently the most important, in particular for television applications.
  • MVA multi-domain vertical alignment, for example: Yoshide, H. et al., Paper 3.1: “MVA LCD for Notebook or Mobile PCs ", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6 to 9 , and Liu, C.T. et al., Paper 15.1: "A 46-inch TFT-LCD HDTV Technology ", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp.
  • PVA patterned vertical alignment, for example: Kim, Sang Soo, Paper 15.4: “Super PVA Sets New State-of-the-Art for LCD-TV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 760 to 763
  • ASV advanced super view, for example: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Paper 15.2: "Development of High Quality LCDTV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754 to 757 ).
  • PAVA photo-alignment VA
  • PSVA polymer-stabilized VA
  • ECB displays like ASV displays, use liquid-crystalline media having negative dielectric anisotropy ( ⁇ ), whereas TN and to date all conventional IPS displays use liquid-crystalline media having positive dielectric anisotropy.
  • IPS and FFS displays utilizing dielectrically negative liquid crystalline media.
  • liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electrical voltage.
  • liquid-crystal media which are generally predominantly composed of liquid-crystal compounds, all of which have the same sign of the dielectric anisotropy and have the highest possible value of the dielectric anisotropy.
  • at most relatively small proportions of neutral compounds and if possible no compounds having a sign of the dielectric anisotropy which is opposite to that of the medium are employed.
  • liquid-crystal media having negative dielectric anisotropy e.g. for ECB or UB-FFS displays
  • predominantly compounds having negative dielectric anisotropy are thus employed.
  • the respective liquid-crystalline media employed generally consist predominantly and usually even essentially of liquid-crystal compounds having negative dielectric anisotropy.
  • Liquid crystalline media having a positive dielectric anisotropy for IPS and FFS displays have already been disclosed. In the following some examples will be given.
  • CN 104232105 A discloses liquid crystalline media with a positive dielectric anisotropy having dielectric ratios ( ⁇ / ⁇ ) of up to 0.7.
  • WO 2014/192390 also discloses liquid crystalline media with a positive dielectric anisotropy having rather high values of ⁇ ⁇ , but having dielectric ratios ( ⁇ / ⁇ ) of only about 0.5.
  • WO 2015/007173 discloses liquid crystalline media with a positive dielectric anisotropy, some of which have a dielectric ratio ( ⁇ / ⁇ ) of about 0.7 and slightly above, up to 0.88.
  • Laid open DE 102016003902.3 , EP 3 081 620 and EP 3 095 834 are related to liquid crystal compounds respectively liquid crystalline media for application in respective displays.
  • EP 17164891.8 , EP 16190393.5 , EP 16194162.0 , EP 16197206.2 and EP 16199580.8 of the applicant of the instant application are also related to liquid crystal compounds respectively liquid crystalline media for application in respective displays.
  • the range of the nematic phase of the liquid-crystal mixture must be sufficiently broad for the intended application of the display.
  • the response times of the liquid-crystal media in the displays also have to be improved, i.e. reduced. This is particularly important for displays for television or multimedia applications.
  • optimise the rotational viscosity of the liquid-crystal media ( ⁇ 1) i.e. to achieve media having the lowest possible rotational viscosity.
  • the results achieved here are inadequate for many applications and therefore make it appear desirable to find further optimisation approaches.
  • Adequate stability of the media to extreme loads, in particular to UV exposure and heating, is very particularly important. In particular in the case of applications in displays in mobile equipment, such as, for example, mobile telephones, this may be crucial.
  • the MLC displays disclosed hitherto have further disadvantages. These are e.g. their comparatively low contrast, their relatively high viewing-angle dependence and the difficulty in the reproduction of grey scales in these displays, especially when observed from an oblique viewing angle, as well as their inadequate VHR and their inadequate lifetime.
  • the desired improvements of the transmission of the displays and of their response times are required in order to improve their energy efficiency, respectively their capacity to render rapidly moving pictures.
  • the invention has the object of providing MLC displays, not only for monitor and TV applications, but also for mobile applications such as e.g. telephones and navigation systems, which are based on the ECB, IPS or FFS effect, do not have the disadvantages indicated above, or only do so to a lesser extent, and at the same time have very high specific resistance values. In particular, it must be ensured for mobile telephones and navigation systems that they also work at extremely high and extremely low temperatures.
  • liquid-crystal displays which have, in particular in IPS and FFS displays, a low threshold voltage with short response times, a sufficiently broad nematic phase, favourable, relatively low birefringence ( ⁇ n) and, at the same time, a high transmission, good stability to decomposition by heating and by UV exposure, and a stable, high VHR if use is made in these display elements of nematic liquid-crystal mixtures which comprise at least one compound, preferably two or more compounds of formula T, preferably selected from the group of the compounds of the sub-formulae T-1 and T-2 and optionally of formula I, preferably selected from I-1, I-2, I-3, I-4 and I-S-1 and/ or I-S-2, particularly preferably of these of the sub-formulate I-2 and/or I-3 and/or I-4 and/or I-S-1 and/or I-S-2, more preferably I-2 and/or I-4 and/or I-S-1 and/or
  • Media of this type can be used, in particular, for electro-optical displays having active-matrix addressing for IPS - or FFS displays.
  • the media according to the present invention preferably additionally comprise a one or more compounds selected from the group of compounds of formulae II and III, preferably one or more compounds of formula II, more preferably in addition one or more compounds of formula III and, most preferably, additionally one or more compounds selected from the group of the compounds of formulae IV and V and, again preferably, one or more compounds selected from the group of compounds of formulae VI to IX (all formulae as defined below).
  • the mixtures according to the invention exhibit very broad nematic phase ranges with clearing points ⁇ 70°C, very favourable values for the capacitive threshold, relatively high values for the holding ratio and at the same time good low-temperature stabilities at -20°C and -30°C, as well as very low rotational viscosities.
  • the mixtures according to the invention are furthermore distinguished by a good ratio of clearing point and rotational viscosity and by a relatively high positive dielectric anisotropy.
  • LCs of the FFS type using liquid crystals with positive dielectric anisotropy may be realised using specially selected liquid crystalline media.
  • These media are characterised by a particular combination of physical properties.
  • Most decisive amongst these are their dielectric properties and here a high average dielectric constant ( ⁇ av. ), a high dielectric constant perpendicular to the director of the liquid crystal molecules ( ⁇ ), a high value of the dielectric anisotropy ( ⁇ ), and, in particular, the relatively high ratio of these latter two values: ( ⁇ / ⁇ ).
  • the liquid crystalline media according to the present invention preferably have a positive dielectric anisotropy, preferably in the range from 1.5 or more to 20.0 or less, more preferably in the range from 3.0 or more to 8.0 or less and, most preferably in the range from 4.0 or more to 7.0. or less.
  • the liquid crystalline media according to the present invention preferably have a dielectric constant perpendicular to the director of the liquid crystal molecules ( ⁇ ) of 5.0 or more, more preferably of 6.0 or more, more preferably of 7.0 or more, more preferably of 8.0 or more, more preferably of 9 or more and, most preferably, of 10.0 or more.
  • the liquid crystalline media according to the present invention preferably have a dielectric ratio ( ⁇ / ⁇ ) of 0.65 or more, more preferably of 0.75 or more and, most preferably, of 1.0 or more.
  • the liquid crystalline medium preferably having a dielectric anisotropy ( ⁇ ) of 0.5 or more, preferably comprises
  • liquid-crystalline media in accordance with the present application preferably have a nematic phase.
  • the present invention also concerns the compouds of formula T, as shown above wherein the parameters have the respective meanings given above and
  • the compounds of formula T which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae T-1 and T-2: in which
  • the compounds of formula T-1 which are used in the liquid crystalline media according to the present application, are selected from the group of compounds of formulae T-1-1 to T-1-4: wherin the parametes have the respective meanings given above.
  • the compounds of formula T-2 are selected from the group of compounds of formulae T-2-1 to T-2-4: wherin the parametes have the respectivreemeanings given above.
  • the compounds of formula T e.g. of formulae PGU-n-X, PUS-n-X and PYS-n-X, are prepared according to the following synthetic route as shown in Scheme 1.
  • a key reaction step being the metallation and bromination of a fluorinated biphenyl derivative in the ortho position, followed by its addition to a respective polar thiophene boronic acid or an ester of a thiophene boronic acid to give the corresponding bisaryl thiophene compound having three cylic (i.e. ring) moieties via a Suzuki coupling.
  • R 1 has the respective meaning of R S and R 2 denotes in each occurrence independently of one another H or F, preferably one of R 2 denotes H and the other one denotes F.
  • one of R 2 may denote an alkyl group, preferably having 1 to 3 C atoms, more preferably methyl or ethyl and most preferably mehyl.
  • the compounds of formula T are prepared according to the following synthetic route as shown in Scheme 2. Also here a key reaction step being a Suzuki coupling.
  • R 1 has the respective meaning of R S .
  • the invention thus also encompasses a process for the preparation of compounds of the formula T, as shown in Scheme 1, which is characterised in that it comprises a process step being the ortho- metallation/bromination of a biphenyl, which is substituted by fluorine, and its subsequent (Suzuki) coupling with a thiophene boronic acid or with an ester of a thiophene boronic acid, as the case may be.
  • the compounds of formula I comprising a dibenzopheneone moiety are selected from the group of compounds of formulae I-S-1 and I-S-2: in which
  • the compounds of formula I comprising a dibenzopheneone moiety, and in particular of formulae I-S-1 and I-S-2, may be prepared via various synthetic route.
  • the essential step is in all cases the formation of the S-heterocyclic ring system via successive Migita coupling and closure of the ring induced by a base.
  • These reactions optionally, and in many cases beneficially, may be performed as a "one pot" (or “single pot") reaction.
  • X 1 F, CF 3 or OCF 3 ;
  • R ethyl or 2-ethylhexyl,
  • R 1 alkyl or, in case of 1,4-cyclohexenylene compound, alternatively also alkenyl.
  • cyclohexanone compound instead of the cyclohexanone compound also a respective cyclohexylcyclohexanone derivative may be used.
  • X 1 F, CF 3 or OCF 3 ;
  • R ethyl or 2-ethylhexyl,
  • R 1 alkyl or alkenyl.
  • the product may be hydrogenated, leading to the corresponding 1,4-cyclohexylene compound and instead of the cyclohexanone compound also a respective cyclohexylcyclohexanone derivative may be used.
  • the present invention in an embodiment also encompasses one or more processes for the preparation of compounds of the formulae I-S-1 and I-S-2.
  • the invention thus encompasses a process for the preparation of compounds of the formula I comprising a dibenzopheneone moiety, which is characterised in that it comprises a process step in which a compound of the formula II is converted into compounds of the formulae I-S-1 and I-S-2 in the presence of a base, as shown in Scheme C3 and in which R, A, Z, X 1 , X 2 , W and m have the meaning indicated above and G denotes -OH, -SH or SG' and G' denotes a base-labile protecting group for thiols.
  • Preferred protecting groups are acetyl, dimethylaminocarbonyl, 2-tetrahydropyranyl, ethoxycarbonylethyl, tert-butyl, methyl and 2-ethylhexyloxycarbonylethyl, particularly preferably ethoxycarbonylethyl or 2-ethylhexyloxycarbonylethyl.
  • the process and the subsequent work-up of the reaction mixture can basically be carried out as a batch reaction or in a continuous reaction procedure.
  • the continuous reaction procedure encompasses, for example, reaction in a continuous stirred-tank reactor, a stirred-reactor cascade, a loop or cross-flow reactor, a flow tube or in a micro reactor.
  • the reaction mixtures are optionally worked up, as necessary, by filtration via solid phases, chromatography, separation between immiscible phases (for example extraction), adsorption onto solid supports, removal of solvents and/or azeotropic mixtures by distillation, selective distillation, sublimation, crystallisation, co-crystallisation or by nanofiltration on membranes.
  • the invention furthermore relates to the use of liquid-crystal mixtures and liquid-crystalline media according to the invention in IPS and FFS displays, in particular the use in SG-FFS displays containing a liquid-crystalline medium, for improving the response times and/or the transmission.
  • the invention furthermore relates to a liquid-crystal display containing a liquid-crystalline medium according to the invention, in particular an IPS or FFS display, particularly preferably a FFS or SG-FFS display.
  • the invention furthermore relates to a liquid-crystal display of the IPS or FFS type comprising a liquid-crystal cell consisting of two substrates, where at least one substrate is transparent to light and at least one substrate has an electrode layer, and a layer, located between the substrates, of a liquid-crystalline medium comprising a polymerised component and a low-molecular-weight component, where the polymerised component is obtainable by polymerisation of one or more polymerisable compounds in the liquid-crystalline medium between the substrates of the liquid-crystal cell, preferably with application of an electrical voltage and where the low-molecular-weight component is a liquid-crystal mixture according to the invention as described above and below.
  • the displays in accordance with the present invention are preferably addressed by an active matrix (active matrix LCDs, AMDs for short), preferably by a matrix of thin-film transistors (TFTs).
  • active matrix LCDs active matrix LCDs, AMDs for short
  • TFTs thin-film transistors
  • the liquid crystals according to the invention can also be used in an advantageous manner in displays having other known addressing means.
  • the invention furthermore relates to a process for the preparation of a liquid-crystalline medium according to the invention by mixing one or more compounds of formula I comprising a dibenzopheneone moiety, preferably selected from the group of compounds of formulae I-S-1 and I-S-2 with one or more low-molecular-weight liquid-crystalline compounds, or a liquid-crystal mixture and optionally with further liquid-crystalline compounds and/or additives.
  • one or more compounds of formula I comprising a dibenzopheneone moiety, preferably selected from the group of compounds of formulae I-S-1 and I-S-2 with one or more low-molecular-weight liquid-crystalline compounds, or a liquid-crystal mixture and optionally with further liquid-crystalline compounds and/or additives.
  • FFS FFFS
  • mesogenic group is known to the person skilled in the art and is described in the literature, and denotes a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquid-crystalline (LC) phase in low-molecular-weight or polymeric substances.
  • Compounds containing mesogenic groups do not necessarily have to have a liquid-crystalline phase themselves. It is also possible for mesogenic compounds to exhibit liquid-crystalline phase behaviour only after mixing with other compounds and/or after polymerisation. Typical mesogenic groups are, for example, rigid rod- or disc-shaped units.
  • spacer group or "spacer” for short, also referred to as “Sp” above and below, is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001 ) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368 . Unless indicated otherwise, the term “spacer group” or “spacer” above and below denotes a flexible group which connects the mesogenic group and the polymerisable group(s) to one another in a polymerisable mesogenic compound.
  • liquid-crystalline medium is intended to denote a medium which comprises a liquid-crystal mixture and one or more polymerisable compounds (such as, for example, reactive mesogens).
  • liquid-crystal mixture (or “host mixture) is intended to denote a liquid-crystalline mixture which consists exclusively of unpolymerisable, low-molecular-weight compounds, preferably of two or more liquid-crystalline compounds and optionally further additives, such as, for example, chiral dopants or stabilisers.
  • liquid-crystal mixtures and liquid-crystalline media which have a nematic phase, in particular at room temperature.
  • the liquid-crystal medium comprises one or more compounds of formula I, preferably selected from the group of compounds of formulae I-1 to I-4 and I-S-1 and I-S-2 in which the parameters have the meanings given above and preferably
  • the liquid-crystal medium comprises one or more compounds of formula I-S0, preferably selected from the group of compounds of formulae S0-1 and S0-2 in which the parameters have the meanings given above and preferably
  • the liquid-crystal medium comprises one or more, preferably dielectrically positive, compounds preferably having a dielectric anisotropy of 3 or more, selected from the group of the compounds of the formulae II-1 and II-2: in which the parameters have the respective meanings indicated above under formula II, and L 23 and L 24 , independently of one another, denote H or F, preferably L 23 denotes F, and has one of the meanings given for and, in the case of formulae II-1 and II-2, X 2 preferably denotes F or OCF 3 , particularly preferably F, and, in the case of formula II-2, and independently of one another, preferably denote and/or selected from the group of the compounds of the formulae III-1 and III-2: in which the parameters have the meanings given under formula III, and the media in accordance with the present invention may comprise, alternatively or in addition to the compounds of the formulae III-1 and/or III-2, one or more compounds of the formula III-3 in which the parameters have the respective meanings indicated
  • the liquid-crystal medium preferably comprises compounds selected from the group of the compounds of the formulae II-1 and II-2 in which L 21 and L 22 and/or L 23 and L 24 both denote F.
  • the liquid-crystal medium comprises compounds selected from the group of the compounds of the formulae II-1 and II-2 in which L 21 , L 22 , L 23 and L 24 all denote F.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula II-1.
  • the compounds of the formula II-1 are preferably selected from the group of the compounds of the formulae II-1a to II-1 e, preferably one or more compounds of formulae) I-1a and/or II-1b and/or II-1d, preferably of formula II-1a and/or II-1d or II-1b and/or II-1d, most preferably of formula II-1d:
  • the liquid-crystal medium preferably comprises one or more compounds of the formula II-2, which are preferably selected from the group of the compounds of the formulae II-2a to II-2k, preferably one or more compounds each of formulae II-2a and/or II-2h and/or II-2j: in which the parameters have the respective meanings indicated above, and L 25 to L 28 , independently of one another, denote H or F, preferably L 27 and L 28 both denote H, particularly preferably L 26 denotes H.
  • the liquid-crystal medium preferably comprises compounds selected from the group of the compounds of the formulae II-1 a to II-1 e in which L 21 and L 22 both denote F and/or L 23 and L 24 both denote F.
  • the liquid-crystal medium comprises compounds selected from the group of the compounds of the formulae II-2a to II-2k in which L 21 , L 22 , L 23 and L 24 all denote F.
  • Especially preferred compounds of the formula II-2 are the compounds of the following formulae, particularly preferred of formulae II-2a-1 and/or II-2h-1 and/or II-2k-2: in which R 2 and X 2 have the meanings indicated above, and X 2 preferably denotes F.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1.
  • the compounds of the formula III-1 are preferably selected from the group of the compounds of the formulae III-1a to III-1j, preferably from formulae III-1c, III-1f, III-1g and III-1j: in which the parameters have the meanings given above and preferably in which the parameters have the respective meanings indicated above, the parameters L 35 and L 36 , independently of one another and of the other parameters, denote H or F, and the parameters L 35 and L 36 , independently of one another and of the other parameters, denote H or F.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1c, which are preferably selected from the group of the compounds of the formulae III-1 c-1 to III-1 c-5, preferably of formulae III-1c-1 and/or III-1c-2, most preferably of formula III-1c-1: in which R 3 has the meaning indicated above.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1f, which are preferably selected from the group of the compounds of the formulae III-1f-1 to III-1f-6, preferably of formulae III-1f-1 and/or III-1f-2 and/or III-1f-3 and /or III-1f-6, more preferably of formula III-1f-3 and/or III-1f-6, more preferably of formula III-1f-6: in which R 3 has the meaning indicated above.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1g, which are preferably selected from the group of the compounds of the formulae III-1g-1 to III-1g-5, preferably of formula III-1g-3: in which R 3 has the meaning indicated above.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1h, which are preferably selected from the group of the compounds of the formulae III-1h-1 to III-1h-3, preferably of the formula III-1h-3: in which the parameters have the meanings given above, and X 3 preferably denotes F.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1i, which are preferably selected from the group of the compounds of the formulae III-1i-1 and III-1i-2, preferably of the formula III-1i-2: in which the parameters have the meanings given above, and X 3 preferably denotes F.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-1j, which are preferably selected from the group of the compounds of the formulae III-1j-1 and III-1j-2, preferably of the formula III-1j-1: in which the parameters have the meanings given above.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-2.
  • the compounds of the formula III-2 are preferably selected from the group of the compounds of the formulae III-2a and III-2b, preferably of formula III-2b: in which the parameters have the respective meanings indicated above, and the parameters L 33 and L 34 , independently of one another and of the other parameters, denote H or F.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-2a, which are preferably selected from the group of the compounds of the formulae III-2a-1 to III-2a-6: in which R 3 has the meaning indicated above.
  • the liquid-crystal medium preferably comprises one or more compounds of the formula III-2b, which are preferably selected from the group of the compounds of the formulae III-2b-1 to III-2b-4, preferably III-2b-4: in which R 3 has the meaning indicated above.
  • the media in accordance with the present invention may comprise one or more compounds of the formula III-3 in which the parameters have the respective meanings indicated above under formula III.
  • the liquid-crystalline media in accordance with the present invention preferably comprise one or more dielectrically neutral compounds, preferably having a dielectric anisotropy in the range from -1.5 to 3, preferably selected from the group of the compounds of the formulae VI, VII, VIII and IX.
  • the elements all include their respective isotopes.
  • one or more H in the compounds may be replaced by D, and this is also particularly preferred in some embodiments.
  • a correspondingly high degree of deuteration of the corresponding compounds enables, for example, detection and recognition of the compounds. This is very helpful in some cases, in particular in the case of the compounds of formula I.
  • the media according to the invention in each case comprise one or more compounds of formula VI selected from the group of the compounds of the formulae VI-1 and VI-2, preferably one or more compounds each of formulae VI-1 and one or more compounds of formula VI-2, in which the parameters have the respective meanings given above under formula VI, and preferably
  • the media according to the invention in each case comprise one or more compounds of formula VII selected from the group of the compounds of the formulae VII-1 to VII-3, preferably one or more compounds each of the formulae VII-1 and one or more compounds of formula VII-2, in which the parameters have the respective meanings given above under formula VII, and preferably
  • the media according to the invention in each case comprise one or more compounds of formula VI-1 selected from the group of the following compounds:
  • the media according to the invention in each case comprise one or more compounds of formula VI-2 selected from the group of the following compounds:
  • the media according to the invention in each case comprise one or more compounds of formula VII-1 selected from the group of the following compounds:
  • the media according to the invention in each case comprise one or more compounds of formula VII-2 selected from the group of the following compounds:
  • the media in accordance with the present invention preferably comprise one or more, preferably dielectrically neutral, compounds selected from the group of compounds of the formulae VI and VII, preferably in a total concentration in the range from 5% or more to 90% or less, preferably from 10% or more to 80% or less, particularly preferably from 20% or more to 70% or less.
  • the media according to the invention in each case comprise one or more compounds of formula VIII selected from the group of the compounds of the formulae VIII-1 to VIII-3, preferably one or more compounds each of the formulae VIII-1 and/or one or more compounds of formula VIII-3, in which the parameters have the respective meanings given above under formula VIII, and preferably
  • R 82 denotes preferably alkoxy having 2 or 4 C atoms and, most preferably, ethoxy and in formula VIII-3 it denotes preferably alkyl, preferably methyl, ethyl or n-propyl, most preferably methyl.
  • the medium comprises one or more compounds of formula IV one or more compounds of formula IV in which
  • the medium comprises one or more compounds of formula IV selected from the group of the compounds of the formulae IV-1 to IV-4, preferably of formula IV-1, in which
  • the media according to the invention comprise one or more compounds of formula IV-1 and/or one or more compounds of formula IV-2.
  • the medium comprises one or more compounds of formula V.
  • the media according to the invention preferably comprise the following compounds in the total concentrations indicated:
  • the media in accordance with the present invention in addition to the compounds of formula T or the preferred sub-formulae thereof, and/or of formula I or the preferred sub-formulae thereof and to the compounds of formulae VI and/or VII and/or VIII and/or IX, preferably comprise one or more, preferably dielectrically neutral, compounds selected from the group of compounds of formulae IV and V preferably in a total concentration in the range from 5 % or more to 90 % or less, preferably from 10 % or more to 80 % or less, particularly preferably from 20 % or more to 70 % or less.
  • the concentration of the compounds of formula T in the media according to the invention is in the range from 1 % or more to 60 % or less, more preferably from 5 % or more to 40 % or less, most preferably from 8 % or more to 35 % or less
  • the concentration of the compounds of formula I is in the range from 1 % or more to 60 % or less, more preferably from 5 % or more to 40 % or less, most preferably from 8 % or more to 35 % or less
  • the media comprise one or more compounds of formula I comprising a dibenzopheneone moiety, preferably selected from the group of formulae I-S-1 and I-S-2 and one or more compounds of formula I, preferably selected from the group of formulae I-1 to I-4, preferably of formulae I-3 and/or I-4.
  • the concentration of the compounds of formula I comprising a dibenzopheneone moiety in the media according to the invention is in the range from 1 % or more to 60 % or less, more preferably from 5 % or more to 40 % or less, most preferably from 8 % or more to 35 % or less
  • the concentration of the compounds of formula II in the media is in the range from 3 % or more to 60 % or less, more preferably from 5 % or more to 55 % or less, more preferably from 10 % or more to 50 % or less and, most preferably, from 15 % or more to 45 % or less.
  • the concentration of the compounds of formula VII in the media is in the range from 2 % or more to 50 % or less, more preferably from 5 % or more to 40 % or less, more preferably from 10 % or more to 35 % or less and, most preferably, from 15 % or more to 30 % or less.
  • the concentration of the compounds of formula VII-1 in the media is in the range from 1 % or more to 40 % or less, more preferably either from 2 % or more to 35 % or less, or, alternatively, from 15 % or more to 25 % or less.
  • the concentration of the compounds of formula VII-2 in the media is in the range from 1 % or more to 40 % or less, more preferably from 5 % or more to 35 % or less and, most preferably, from 10 % or more to 30 % or less.
  • the present invention also relates to electro-optical displays or electro-optical components which contain liquid-crystalline media according to the invention. Preference is given to electro-optical displays which are based on the VA, ECB, IPS or FFS effect, preferably on the VA; IPS or FFS effect, and in particular those which are addressed by means of an active-matrix addressing device.
  • the present invention likewise relates to the use of a liquid-crystalline medium according to the invention in an electro-optical display or in an electro-optical component, and to a process for the preparation of the liquid-crystalline media according to the invention, characterised in that one or more compounds of formula I are mixed with one or more compounds of formula II, preferably with one or more compounds of the sub-formulae II-1 and/or II-2 and/or with one or more compounds of formula VII, preferably with one or more compounds of the sub-formulae VII-1 and/or VII-2, particularly preferably one or more compounds from two or more, preferably from three or more, different formulae thereof and very particularly preferably from all four of these formulae II-1, II-2, VII-1 and VII-2 and one or more further compounds, preferably selected from the group of the compounds of the formulae IV and V, more preferably with one or more compounds both of formula IV and of formula V.
  • the medium comprises one or more compounds of formula IV, selected from the group of the compounds of the formulae IV-2 and IV-3, in which
  • the medium comprises one or more compounds of formula V selected from the group of the compounds of the formulae V-1 and V-2, preferably of formulae V-1, in which the parameters have the meanings given above under formula V, and preferably
  • the medium comprises one or more compounds of formula V-1 selected from the group of the compounds of the formulae V-1a and V-1b, in which
  • the present invention relates to a method for the reduction of the wavelength dispersion of the birefringence of a liquid-crystalline medium which comprises one or more compounds of formula II, optionally one or more compounds selected from the group of the compounds of the formulae VII-1 and VII-2 and/or one or more compounds of formula IV and/or one or more compounds of formula V, characterised in that one or more compounds of formula I are used in the medium.
  • the media according to the invention may optionally also comprise a dielectrically positive component, whose total concentration is preferably 20 % or less, more preferably 10 % or less, based on the entire medium.
  • liquid-crystal media according to the invention comprise in total, based on the mixture as a whole,
  • liquid-crystal media in accordance with the present invention may comprise one or more chiral compounds.
  • the compounds of formula T which are preferred as such and are used preferably in the liquid crystallime media comprise one or more rings, preferably one ring selected from preferably selected from or most preferably being
  • the media according to the present invention fulfil one or more of the following conditions.
  • the total concentration of the compounds of formula CC-3-V in the mixture as a whole preferably either is 15 % or less, preferably 10 % or less or 20 % or more, preferably 25 % or more.
  • the invention furthermore relates to an electro-optical display having active-matrix addressing based on the VA, ECB, IPS, FFS or UB-FFS effect, characterised in that it contains, as dielectric, a liquid-crystalline medium in accordance with the present invention.
  • the liquid-crystal mixture preferably has a nematic phase range having a width of at least 70 degrees.
  • the rotational viscosity ⁇ 1 is preferably 200 mPa ⁇ s or less, preferably 150 ⁇ s or less and, in particular, 120 mPa ⁇ s or less.
  • the mixtures according to the invention are suitable for all IPS and FFS-TFT applications using dielectrically positive liquid crystalline media, such as, e.g. SG-FFS (Super Grip FFS).
  • dielectrically positive liquid crystalline media such as, e.g. SG-FFS (Super Grip FFS).
  • the liquid-crystalline media according to the invention preferably virtually completely consist of 4 to 18, in particular 5 to 15, and particularly preferably 12 or less, compounds. These are preferably selected from the group of the compounds of the formulae S, I, II III,IV, V, VI, VII, VIII and IX.
  • the liquid-crystalline media according to the invention may optionally also comprise more than 18 compounds. In this case, they preferably comprise 18 to 25 compounds.
  • the liquid-crystal media according to the invention predominantly consist of, preferably essentially consist of and, most preferably, virtually completely consist of compounds which do not comprise a cyano group.
  • the liquid-crystal media according to the invention comprise compounds selected from the group of the compounds of the formulae T, I, II and III, IV and V and VI to IX, preferably selected from the group of the compounds of the formulae T, preferably selected from T-1 and T-2, I, preferably selected from I-1, I-2, I-3 and I-4, I comprising a dibenzopheneone moiety , the latter preferably selected from I-S-1, I-S-2, I-S0, preferably selected from IS0-1 and I-S0-2, II, preferably selected from II-1 and II-2, III, preferably selected from III-1 and III-2, IV, V, VII, preferably selected from VII-1 and VII-2, VIII and IX; they preferably consist predominantly, particularly preferably essentially and very particularly preferably virtually completely of the compounds of the said formulae.
  • the liquid-crystal media according to the invention preferably have a nematic phase from in each case at least -10°C or less to 70°C or more, particularly preferably from -20°C or less to 80°C or more, very particularly preferably from -30°C or less to 85°C or more and most preferably from -40°C or less to 90°C or more.
  • the expression "have a nematic phase” here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating out of the nematic phase.
  • the investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a cell thickness corresponding to the electro-optical application for at least 100 hours. If the storage stability at a temperature of -20°C in a corresponding test cell is 1000 h or more, the medium is regarded as stable at this temperature. At temperatures of -30°C and -40°C, the corresponding times are 500 h and 250 h respectively. At high temperatures, the clearing point is measured in capillaries by conventional methods.
  • the liquid-crystal media according to the invention are characterised by optical anisotropy values in the moderate to low range.
  • the birefringence values are preferably in the range from 0.075 or more to 0.130 or less, particularly preferably in the range from 0.085 or more to 0.120 or less and very particularly preferably in the range from 0.090 or more to 0.115 or less.
  • the liquid-crystal media according to the invention have a positive dielectric anisotropy and relatively high absolute values of the dielectric anisotropy ⁇ , which preferably is in the range from 0.5 or more, preferably of 1.0 or more, more preferably of 2.0 or more to 20 or less, more preferably to 15 or less, more preferably from 3.0 or more to 10 or less, particularly preferably from 4.0 or more to 9.0 or less and very particularly preferably from 4.5 or more to 8.0 or less.
  • the liquid-crystal media according to the invention preferably have relatively low values for the threshold voltage (Va) in the range from 1.0 V or more to 2.7 V or less, preferably from 1.2 V or more to 2.5 V or less, particularly preferably from 1.3 V or more to 2.2 V or less.
  • Va threshold voltage
  • the liquid-crystal media according to the invention preferably have relatively high values of the average dielectric constant ( ⁇ av. ⁇ ( ⁇ + 2 ⁇ )/3) which are preferably in the range from 4.0 or more to 25.0 or less, preferably from5.0 or more to 20.0 or less, still more preferably from 6.0 or more to 19.0 or less, particularly preferably from 10.0 or more to 18.0 or less and very particularly preferably from 9.0 or more to 16.5 or less.
  • the average dielectric constant ⁇ av. ⁇ ( ⁇ + 2 ⁇ )/3
  • liquid-crystal media according to the invention have high values for the VHR in liquid-crystal cells.
  • these values of the VHR are greater than or equal to 95 %, preferably greater than or equal to 97 %, particularly preferably greater than or equal to 98 % and very particularly preferably greater than or equal to 99 %, and after 5 minutes in the oven at 100°C in the cells, these are greater than or equal to 90 %, preferably greater than or equal to 93 %, particularly preferably greater than or equal to 96 % and very particularly preferably greater than or equal to 98 %.
  • liquid-crystal media having a low addressing voltage or threshold voltage here have a lower VHR than those having a higher addressing voltage or threshold voltage, and vice versa.
  • liquid-crystalline media according to the invention comprise:
  • the media according to the invention comprise one or more compounds of formula IX,
  • the media according to the invention comprise one or more compounds of formula IX selected from one or more formulae of the group of the compounds of the formulae IX-1 to IX-4, very particularly preferably of the formulae IX-1 to IX-3, in which the parameters have the meanings given under formula IX.
  • the medium comprises one or more compounds of formula IX-3, preferably of formula IX-3-a, in which alkyl and alkyl', independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms.
  • the compounds of formula IX are used in the liquid crystalline media according to the present application, they are preferably present in a concentration of 20 % or less, more preferably of 10 % or less and, most preferably, of 5 % or less and for the individual i.e. (homologous) compounds preferably in a concentration of 10 % or less and, more preferably, of 5 % or less.
  • the concentration of the compound in question is preferably 1% or more, particularly preferably 2% or more, very particularly preferably 4% or more.
  • ⁇ means less than or equal to, preferably less than, and " ⁇ " means greater than or equal to, preferably greater than.
  • trans -1,4-cyclohexylene denotes 1,4-cyclohexylene, preferably trans -1,4-cyclohexylene , and denote 1,4-phenylene.
  • the expression “dielectrically positive compounds” means compounds having a ⁇ of > 1.5
  • the expression “dielectrically neutral compounds” generally means those where -1.5 ⁇ ⁇ ⁇ 1.5
  • the expression “dielectrically negative compounds” means those where ⁇ ⁇ -1.5.
  • the dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture in each case in at least one test cell having a cell thickness of 20 ⁇ m with homeotropic and with homogeneous surface alignment at a temperature of 20°C and at a frequency of 1 kHz.
  • the measurement voltage is typically 1.0 V, but is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
  • the host mixture used for dielectrically positive and dielectrically neutral compounds is ZLI-4792 and that used for dielectrically negative compounds is ZLI-2857, both from Merck KGaA, Germany.
  • the values for the respective compounds to be investigated are obtained from the change in the dielectric constant of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed.
  • the compound to be investigated is dissolved in the host mixture in an amount of 10%. If the solubility of the substance is too low for this purpose, the concentration is halved in steps until the investigation can be carried out at the desired temperature.
  • the liquid-crystal media according to the invention may, if necessary, also comprise further additives, such as, for example, stabilisers and/or pleochroitic, e.g. dichroitic, dyes and/or chiral dopants in the usual amounts.
  • the amount of these additives employed is preferably in total 0 % or more to 10 % or less, based on the amount of the entire mixture, particularly preferably 0.1 % or more to 6 % or less.
  • the concentration of the individual compounds employed is preferably 0.1 % or more to 3 % or less. The concentration of these and similar additives is generally not taken into account when specifying the concentrations and concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
  • the liquid-crystal media according to the invention comprise a polymer precursor which comprises one or more reactive compounds, preferably reactive mesogens, and, if necessary, also further additives, such as, for example, polymerisation initiators and/or polymerisation moderators, in the usual amounts.
  • the amount of these additives employed is in total 0 % or more to 10 % or less, based on the amount of the entire mixture, preferably 0.1 % or more to 2 % or less.
  • concentration of these and similar additives is not taken into account when specifying the concentrations and concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
  • compositions consist of a plurality of compounds, preferably 3 or more to 30 or fewer, particularly preferably 6 or more to 20 or fewer and very particularly preferably 10 or more to 16 or fewer compounds, which are mixed in a conventional manner.
  • the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent of the mixture. This is advantageously carried out at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, completion of the dissolution operation is particularly easy to observe.
  • the mixtures according to the invention exhibit very broad nematic phase ranges having clearing points of 65°C or more, very favourable values for the capacitive threshold, relatively high values for the voltage holding ratio (VHR) and at the same time very good low-temperature stabilities at -30°C and -40°C. Furthermore, the mixtures according to the invention are distinguished by low rotational viscosities ⁇ 1.
  • the media according to the invention for use in VA, IPS, FFS or PALC displays may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.
  • the structure of the liquid-crystal displays according to the invention corresponds to the usual geometry, as described, for example, in EP-A 0 240 379 .
  • liquid-crystal phases according to the invention can be modified by means of suitable additives in such a way that they can be employed in any type of, for example, IPS and FFS LCD display that has been disclosed to date.
  • Table E below indicates possible dopants which can be added to the mixtures according to the invention. If the mixtures comprise one or more dopants, it is (they are) employed in amounts of 0.01 % to 4 %, preferably 0.1 % to 1.0 %.
  • Stabilisers which can be added, for example, to the mixtures according to the invention, preferably in amounts of 0.01 % to 6 %, in particular 0.1 % to 3 %, are shown below in Table F.
  • threshold voltage relates to the capacitive threshold (V 0 ), also known as the Freedericks threshold, unless explicitly indicated otherwise.
  • the electro-optical properties for example the threshold voltage (V 0 ) (capacitive measurement), are, as is the switching behaviour, determined in test cells produced at Merck Japan.
  • the measurement cells have soda-lime glass substrates and are constructed in an ECB or VA configuration with polyimide alignment layers (SE-1211 with diluent **26 (mixing ratio 1:1), both from Nissan Chemicals, Japan), which have been rubbed perpendicularly to one another and effect homeotropic alignment of the liquid crystals.
  • the surface area of the transparent, virtually square ITO electrodes is 1 cm 2 .
  • a chiral dopant is not added to the liquid-crystal mixtures used, but the latter are also particularly suitable for applications in which doping of this type is necessary.
  • the rotational viscosity is determined using the rotating permanent magnet method and the flow viscosity in a modified Ubbelohde viscometer.
  • the rotational viscosity values determined at 20°C are 161 mPa ⁇ s, 133 mPa ⁇ s and 186 mPa ⁇ s respectively, and the flow viscosity values (v) are 21 mm 2 ⁇ s -1 , 14 mm 2 ⁇ s -1 and 27 mm 2 ⁇ s -1 , respectively.
  • the dispersion of the refractive index of the materials may for practical purposes be conveniently characterized in the following way, which is used throughout this application unless explicitly stated otherwise.
  • the values of the birefringence are determined at a temperature of 20°C at several fixed wavelengths using a modified Abbe refractometer with homeotropically aligning surfaces on the sides of the prisms in contact with the material.
  • the birefringence values are determined at the specific wavelength values of 436 nm (respective selected spectral line of a low pressure mercury lamp), 589 nm (sodium "D" line) and 633 nm (wavelength of a HE-Ne laser (used in combination with an attenuator/diffusor in order to prevent damage to the eyes of the observers.
  • n H 2n+1 , C m H 2m+1 and C 1 H 2l+1 or C n H 2n , C m H 2m and C l H 2l are straight-chain alkyl radicals or alkylene radicals, in each case having n, m and l C atoms respectively.
  • n, m and l are independently of each other 1, 2, 3, 4, 5, 6, or 7.
  • Table A shows the codes for the ring elements of the nuclei of the compound
  • Table B lists the bridging units
  • Table C lists the meanings of the symbols for the left- and right-hand end groups of the molecules.
  • the acronyms are composed of the codes for the ring elements with optional linking groups, followed by a first hyphen and the codes for the left-hand end group, and a second hyphen and the codes for the right-hand end group.
  • Table D shows illustrative structures of compounds together with their respective abbreviations.
  • the mixtures according to the invention preferably comprise one or more compounds of the compounds mentioned below.
  • n, m and l are, independently of one another, each an integer, preferably 1 to 6, l possibly also 0 and preferably 0 or 2).
  • Table D Exemplary, preferably used compounds comprising a thiophene ring
  • Exemplary, preferred compounds of formula I comprising a dibenzopheneone moiety having a high ⁇ :
  • Table E shows chiral dopants which are preferably employed in the mixtures according to the invention.
  • the media according to the invention comprise one or more compounds selected from the group of the compounds from Table E.
  • Table F shows stabilisers which can preferably be employed in the mixtures according to the invention in addition to the compounds of formula I.
  • the parameter n here denotes an integer in the range from 1 to 12.
  • the phenol derivatives shown can be employed as additional stabilisers since they act as antioxidants.
  • the media according to the invention comprise one or more compounds selected from the group of the compounds from Table F, in particular one or more compounds selected from the group of the compounds of the following two formulae
  • Step 1.1 1,3-Difluoro-5-(4-propylphenyl)benzene
  • Step 1.2 2-Bromo-1,3-difluoro-5-(4-propylphenyl)benzene
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo.
  • the residue is purified by silica gel chromatography (solvent heptane) to give 2-bromo-1,3-difluoro-5-(4-propylphenyl)benzene ( 4 ) as a colorless oil.
  • Step 1.3 2-[2,6-difluoro-4-(4-propylphenyl)phenyl]-5-(trifluoromethyl)thiophene
  • Compound ( 6 ) has the following phase characteristics: K 39°C SmA 137°C I.
  • Step 2.1 2-[2,6-Difluoro-4-(4-propylphenyl)phenyl]-5-fluoro-thiophene
  • Compound (8) has the following phase characteristics: K 67°C S A 76°C N 102°C I.
  • Step C-1.1 3,2',3'-Trifluoro-4'-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ol
  • reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20°C, typically (20 ⁇ 1)°C.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane/heptane 1:1). 3,2',3'-Trifluoro-4'-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ol ( 3 ) is isolated as a brown solid.
  • Step C-1.2 Trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-yl ester
  • Trifluoromethanesulfonic anhydride (31 mL, 0.19 mol) is slowly added to a solution of 3,2',3'-trifluoro-4'-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-ol ( 3 ) (66 g, 0.15 mol), TEA (32 mL, 0.23 mol) and DMAP (560 mg, 4.58 mmol) in dichloromethane (500 mL) at 5°C under nitrogen atmosphere. The solution is stirred at room temperature overnight.
  • reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-yl ester ( 4 ) as a brown oil.
  • Step C-1.3 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethoxy-dibenzothiophene
  • This reaction is performed as a one-pot reaction.
  • a solution of trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propyl-cyclohex-1-enyl)-4-trifluoromethoxy-biphenyl-2-yl ester ( 4 ) (87 g, 0.15 mol), 3-mercapto-propionic acid 2-ethylhexyl ester (45 mL, 0.19 mol), N -ethyldiisopropylamine (40 mL, 0.24 mol) and toluene (350 mL) is degassed with Argon for 1 h.
  • Tris(dibenzylideneacetone)dipalladium(0) (1.5 g, 1.56 mmol) and (oxydi-2,1-phenylene)bis(diphenylphosphine) (1.6 g, 2.91 mmol) are quickly added to the solution, and the reaction mixture is heated at reflux temperature overnight. Then it is allowed to cool to room temperature.
  • a solution of potassium tert -butylate (22 g, 0.20 mol) in THF (200 mL) is added to the reaction mixture containing intermediate ( 5 ) in situ.
  • reaction mixture is heated at reflux temperature overnight, followed by addition of a second portion of a solution of potassium tert-butylate (11 g, 0.1 mol) in THF (100 mL). The reaction mixture is heated again at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25 %) at 0°C and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo.
  • Compound ( 6 ) has the following phase characteristics: K 66°C SmA 181°C I.
  • Step C-2.1 3,2',3'-Trifluoro-4-trifluoromethyl-biphenyl-2-ol
  • reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20°C, typically (20 ⁇ 1)°C.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent dichloromethane). 3,2',3'-Trifluoro-4-trifluoromethyl-biphenyl-2-ol ( 3 ) is isolated as a brown solid.
  • Step C-2.2 Trifluoromethanesulfonic acid 3,2',3'-trifluoro-4-trifluoromethyl-biphenyl-2-yl ester
  • Trifluoromethanesulfonic anhydride (30.0 mL, 0.18 mol) is slowly added to a solution of 3,2',3'-trifluoro-4-trifluoromethyl-biphenyl-2-ol ( 3 ) (46.8 g, 0.15 mol), TEA (32 mL, 0.23 mol) and DMAP (600 mg, 4.9 mmol) in dichloromethane (300 mL) at 5°C under nitrogen atmosphere. The solution is stirred at room temperature overnight.
  • reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2',3'-trifluoro-4-trifluoromethyl-biphenyl-2-yl ester ( 4 ) as a yellow oil.
  • This reaction is performed as a one-pot reaction.
  • a solution of trifluoromethanesulfonic acid 3,2',3'-trifluoro-4-trifluoromethyl-biphenyl-2-yl ester ( 4 ) (66 g, 0.15 mol) and ethyl 3-mercaptopropionate (24 mL, 0.18 mol) in toluene (500 mL) is heated under nitrogen atmosphere to 80°C.
  • Step C-2.4 1-(4,6-Difluoro-7-trifluoromethyl-dibenzothiophen-3-yl)-4-propyl-cyclohexanol
  • Lithiumdiisopropylamide (6 mL, 2 M in cyclohexane/ethylbenzene/THF, 12 mmol) is added to a solution of 4,6-difluoro-3-trifluoromethyl-dibenzothiophene ( 6 ) (3.2 g, 10 mmol) in THF (100 mL) at -70°C under nitrogen atmosphere.
  • a solution of 4-propylcyclohexanone (1.7 g, 12 mmol) in THF (10 mL) is added after 1 h, and the reaction mixture is stirred for 2 h at -70°C. Then it is allowed to warm to room temperature and is stirred overnight.
  • reaction is quenched with distilled water and hydrochloric acid (25%) at 0°C and diluted with MTB ether.
  • aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo.
  • the residue is purified by silica gel chromatography (solvent dichlormethane) to give 1-(4,6-difluoro-7-trifluoromethyl-dibenzothiophen-3-yl)-4-propyl-cyclohexanol ( 7 ) as yellow crystals.
  • Step C-2.5 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethyl-dibenzothiophene
  • Compound (7) has the following phase characteristics: K 121 °C SmA 162°C I.
  • Step 3.1 3,2',3'-Trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-ol
  • reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20°C, typically (20 ⁇ 1)°C.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane/heptane 1:1). 3,2',3'-Trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-ol ( 3 ) is isolated as a yellow solid.
  • Step C-3.2 Trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propylcyclohexyl)-4-trifluoromethyl-biphenyl-2-yl ester
  • Trifluoromethanesulfonic anhydride (2.8 mL, 17.0 mmol) is slowly added to a solution of 3,2',3'-trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-ol ( 3 ) (5.5 g, 13.2 mmol), TEA (2.8 mL, 20.2 mmol) and DMAP (50 mg, 0.41 mmol) in dichloromethane (50 mL) at 5°C under nitrogen atmosphere. The solution is stirred at room temperature overnight.
  • reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethyl-biphenyl-2-yl ester ( 4 ) as a yellow oil.
  • Step C-3.3 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethyl-dibenzothiophene
  • This reaction is performed as a one-pot reaction.
  • Potassium carbonate (5.0 g, 36.2 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.7 g, 0.73 mmol) and (oxydi-2,1-phenylene)bis(diphenylphosphine) (0.8 g, 1.46 mmol) are quickly added to the solution, and the reaction mixture is heated at reflux temperature overnight. Then it is allowed to cool to room temperature.
  • a solution of potassium tert-butylate (1.8 g, 16.0 mmol) in THF (20 mL) is added to the reaction mixture containing intermediate ( 5 ) in situ.
  • reaction mixture is heated at reflux temperature overnight, followed by addition of a second portion of a solution of potassium tert-butylate (1.8 g, 16.0 mmol) in THF (20 mL). The reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25 %) at 0°C and diluted with MTB ether. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo.
  • Compound (6) has the following phase characteristics: K 150°C N (139°C) I
  • 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethyl-dibenzothiophene is obtained by hydrogenation of 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethyl-dibenzothiophene:
  • Step C-4.1 3,2',3'-Trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-ol
  • reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature and diluted with MTB ether and distilled water. Throughout this application, unless explicitly stated otherwise, room temperature and ambient temperature are used synonymously and signify a temperature of about 20°C, typically (20 ⁇ 1)°C.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo. The residue is purified by silica gel chromatography (solvent 1-chlorobutane/heptane 1:1). 3,2',3'-Trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-ol ( 3 ) is isolated as a yellow solid.
  • Step C-4.2 Trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propylcyclohexyl)-4-trifluoromethoxy-biphenyl-2-yl ester
  • Trifluoromethanesulfonic anhydride (6.0 mL, 36.4 mmol) is slowly added to a solution of 3,2',3'-trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-ol ( 3 ) (12.6 g, 29.0 mmol), TEA (6.3 mL, 45.4 mmol) and DMAP (110 mg, 0.9 mmol) in dichloromethane (100 mL) at 5°C under nitrogen atmosphere. The solution is stirred at room temperature overnight.
  • reaction mixture is purified by silica gel chromatography (solvent dichlormethane) to give trifluoromethanesulfonic acid 3,2',3'-trifluoro-4'-(4-propyl-cyclohexyl)-4-trifluoromethoxy-biphenyl-2-yl ester ( 4 ) as a yellow oil.
  • Step C-4.3 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethoxy-dibenzothiophene
  • This reaction is performed as a one-pot reaction.
  • reaction mixture is heated at reflux temperature overnight, followed by addition of a second portion of a solution of potassium tert-butylate (3.5 g, 31.2 mmol) in THF (50 mL).
  • the reaction mixture is heated at reflux temperature overnight. Then it is cooled to room temperature, quenched with distilled water and hydrochloric acid (25 %) at 0°C and diluted with MTB ether.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with distilled water and brine, dried (sodium sulphate) and concentrated in vacuo.
  • Compound ( 6 ) has the following phase characteristics: K 108°C SmA 141°C N 169°C I
  • 4,6-Difluoro-3-(4-propyl-cyclohexyl)-7-trifluoromethoxy-dibenzothiophene is obtained by hydrogenation of 4,6-Difluoro-3-(4-propyl-cyclohex-1-enyl)-7-trifluoromethoxy-dibenzothiophene:
  • Exemplary compounds having a high dielectric constant perpendicular to the director ( ⁇ ) and a high average dielectric constant ( ⁇ av .) are exemplified in the following compound examples.
  • This compound (PGS-3-T) has a melting point of 61°C, a clearing point of 172°C, a phase range of K 61°C Ss 98°C N 172°C I and a ⁇ of + 13.7.
  • This compound (PYS-3-T) has a melting point of 63°C, a clearing point of 146°C, a phase range of K 63°C S A 146°C I and a ⁇ of + 7.7.
  • This compound (PUS-3-T) has a melting point of 67°C, a clearing point of 102°C, a phase range of K 67°C N 102°C I and a ⁇ of + 17.4.
  • This compound (PUS-3-F, reference compound) has a melting point of 67°C, a clearing point of 102°C, a phase range of K 67°C Sa 76°C N 102°C I and a ⁇ of + 10.6.
  • This compound (PS-3-T) has a melting point of 69°C, an extrapolated clearing point of -62°C, a phase range of K 69°C I and a ⁇ of + 9.1 (extrapolated from 5 % solution).
  • This compound (YS-2O-T) has a melting point of 68°C, an extrapolated clearing point of -36°C, a phase range of K 66°C I and a ⁇ of + 5.5.
  • This compound (LB(S)-3-F) has a melting point of 133°C, a clearing point of 155.3°C, a phase range of K 133°C N 155.3°C I and a ⁇ of + 1.3.
  • This compound (LB(S)-3-OT), the compound of synthesis example 2, has a melting point of 66°C, a clearing point of 181°C, a phase range of K 66°C S A 181°C I and a ⁇ of + 4.7.
  • This compound (LB(S)-3-T) has a melting point of 121°C, a clearing point of 162°C, a phase range of 121°C S A 162°C I and a ⁇ of + 7.8.
  • This compound (CB(S)-3-F) has a melting point of 157°C, a clearing point of 170.3°C, a phase range of K 157°C N 170.3 I.
  • This compound (CB(S)-3-OT), the compound of synthesis example 2, has a melting point of 108°C, a clearing point of 168.5°C, a phase range of K 108°C S A 141°C N 168.5°C I and a ⁇ of + 4.5.
  • This compound (CB(S)-3-T) has a melting point of 150°C, a (monotropic) clearing point of 138.8°C, a phase range of K 150°C N (138.8°C) I and a ⁇ of + 8.1.
  • This compound (DB(S)-3-OT) has a melting point of 153°C, a clearing point of 174.1°C and a phase range of K 153°C S A 165°C N 174.1°C I.
  • This compound (DB(S)-3-OT) has a melting point of 146°C, a clearing point of 168°C and a phase range of K 146°C S A 168°C I.
  • This mixture, mixture M-1 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-2 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-3 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-4 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-5 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-6 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-7 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-8 is characterized by a good transmission in an FFS display and shows a short response time.
  • This mixture, mixture M-10 is characterized by a good transmission in an FFS display and shows a short response time.
  • This comparative mixture, mixture A has a dielectric ratio ( ⁇ ⁇ / ⁇ ) of 0.50, a ratio of ( ⁇ 1 / k 11 ) of 4.81 mPa ⁇ s / pN and is characterized a moderately good transmission in an FFS display and shows an at best acceptable short response time.
  • Table 1 Example CE-A A-1 A-2 A-3 Composition Cpd. None PGS-3-T PYS-3-T PUS-3-T c(Cpd.)/% 0.0 10.0 10.0 10.0 c(CE-A)/% 100.0 90.0 90.0 90.0 90.0 Properties T(N, l)/°C 78.5 80.5 78.0 77.8 n e (589 nm) 1.5875 t.b.d.

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Claims (16)

  1. Flüssigkristallines Medium, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen der Formel T
    Figure imgb0632
     enthält, worin
    Figure imgb0633
     bedeutet,
    Figure imgb0634
     unabhängig voneinander
    Figure imgb0635
    Figure imgb0636
     bedeuten,
    bei denen die jeweiligen Ringe, und vorzugsweise die Phenylenringe, gegebenenfalls jeweils durch eine oder zwei Alkylgruppen, vorzugsweise durch Methyl- und/oder Ethylgruppen, vorzugsweise durch eine Methylgruppe substituiert sein können,
    n 1 oder 2 bedeutet,
    RS Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy, vorzugsweise mit 1 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclopropylen, 1,3-Cyclo-butylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclo-pentylen ersetzt sein kann, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclo-propylen, 1,3-Cyclobutylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclopentylen ersetzt sein kann, bedeutet, und
    XS ein fluoriertes Alkyl oder ein fluoriertes Alkoxy, vorzugsweise solche mit 1 bis 4 C-Atomen, stärker bevorzugt CF3 oder OCF3 bedeutet.
  2. Medium nach Anspruch 1, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen der Formel T enthält, die ausgewählt sind aus der Gruppe der Verbindungen der Formeln T-1 und T-2:
    Figure imgb0637
    Figure imgb0638
     worin
    RS Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen bedeutet, und
    XS ein fluoriertes Alkyl oder ein fluoriertes Alkoxy bedeutet.
  3. Medium nach Anspruch 2, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen der Formel T-1 enthält.
  4. Medium nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen enthält, die ausgewählt sind aus der Gruppe der Verbindungen der Formeln II und III:
    Figure imgb0639
    Figure imgb0640
     worin
    R2 Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy mit 1 bis 7 C-Atomen, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen bedeutet,
    Figure imgb0641
     bei jedem Auftreten unabhängig voneinander
    Figure imgb0642
    Figure imgb0643
    Figure imgb0644
    Figure imgb0645
    Figure imgb0646
    Figure imgb0647
     bedeuten,
    L21 und L22 H oder F bedeuten,
    X2 Halogen, halogeniertes Alkyl oder Alkoxy mit 1 bis 3 C-Atomen oder halogeniertes Alkenyl oder Alkenyloxy mit 2 oder 3 C-Atomen bedeutet,
    m 0, 1, 2 oder 3 bedeutet,
    R3 Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy mit 1 bis 7 C-Atomen, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen bedeutet,
    Figure imgb0648
     bei jedem Auftreten unabhängig voneinander
    Figure imgb0649
    Figure imgb0650
    Figure imgb0651
    Figure imgb0652
    Figure imgb0653
    Figure imgb0654
     sind,
    L31 und L32 unabhängig voneinander H oder F bedeuten,
    X3 Halogen, halogeniertes Alkyl oder Alkoxy mit 1 bis 3 C-Atomen oder halogeniertes Alkenyl oder Alkenyloxy mit 2 oder 3 C-Atomen, F, Cl, -OCF3, -OCHF2, -O-CH2CF3, -O-CH=CF2, -O-CH=CH2 oder -CF3 bedeutet,
    Z3 -CH2CH2-, -CF2CF2-, -COO-, trans-CH=CH-, trans-CF=CF-, -CH2O- oder eine Einfachbindung bedeutet, und
    n 0, 1, 2 oder 3 bedeutet.
  5. Flüssigkristallines Medium nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen enthält, die ausgewählt sind aus der Gruppe der Formeln IV und V:
    Figure imgb0655
    Figure imgb0656
     worin
    R41 und R42 unabhängig voneinander die in Anspruch 4 für R2 unter Formel II angegebene Bedeutung besitzen,
    Figure imgb0657
     unabhängig voneinander und, wenn
    Figure imgb0658
     zweimal auftritt, auch diese unabhängig voneinander
    Figure imgb0659
    Figure imgb0660
    Figure imgb0661
    Figure imgb0662
    Figure imgb0663
     bedeuten,
    Z41 und Z42 unabhängig voneinander und, wenn Z41 zweimal auftritt, auch diese unabhängig voneinander -CH2CH2-, -COO-, trans-CH=CH-, trans-CF=CF-, -CH2O-, -CF2O-, -C=C- oder eine Einfachbindung bedeuten,
    p 0, 1 oder 2 bedeutet,
    R51 und R52 unabhängig voneinander eine der für R41 und R42 genannten Bedeutungen besitzen,
    Figure imgb0664
     wenn vorhanden, jeweils unabhängig voneinander
    Figure imgb0665
    Figure imgb0666
    Figure imgb0667
    Figure imgb0668
     bedeuten,
    Z51 bis Z53 jeweils unabhängig voneinander -CH2-CH2-, -CH2-O-, -CH=CH-, -C=C-, -COO- oder eine Einfachbindung bedeuten, und
    i und j jeweils unabhängig voneinander 0 oder 1 bedeuten.
  6. Flüssigkristallines Medium nach Anspruch 5, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen enthält, die ausgewählt sind aus der Gruppe der Formeln VI bis IX:
    Figure imgb0669
    Figure imgb0670
    Figure imgb0671
    Figure imgb0672
     bei denen
    R61 einen unsubstituierten Alkylrest mit 1 bis 7 C-Atomen, einen unsubstituierten Alkenylrest mit 2 bis 7 C-Atomen, einen unsubstituierten Alkoxyrest mit 1 bis 6 C-Atomen oder einen unsubstituierten Alkenyloxyrest mit 2 bis 6 C-Atomen bedeutet,
    R62 einen unsubstituierten Alkylrest mit 1 bis 7 C-Atomen, einen unsubstituierten Alkoxyrest mit 1 bis 6 C-Atomen oder einen unsubstituierten Alkenyloxyrest mit 2 bis 6 C-Atomen bedeutet, und
    I 0 oder 1 bedeutet,
    R71 einen unsubstituierten Alkylrest mit 1 bis 7 C-Atomen oder einen unsubstituierten Alkenylrest mit 2 bis 7 C-Atomen bedeutet,
    R72 einen unsubstituierten Alkylrest mit 1 bis 7 C-Atomen, einen unsubstituierten Alkoxyrest mit 1 bis 6 C-Atomen oder einen unsubstituierten Alkenyloxyrest mit 2 bis 6 C-Atomen bedeutet,
    Figure imgb0673
     oder
    Figure imgb0674
     bedeutet,
    R81 einen unsubstituierten Alkylrest mit 1 bis 7 C-Atomen oder einen unsubstituierten Alkenylrest mit 2 bis 7 C-Atomen bedeutet,
    R82 einen unsubstituierten Alkylrest mit 1 bis 7 C-Atomen, einen unsubstituierten Alkoxyrest mit 1 bis 6 C-Atomen oder einen unsubstituierten Alkenyloxyrest mit 2 bis 6 C-Atomen, vorzugsweise mit 2, 3 oder 4 C-Atomen, bedeutet,
    Figure imgb0675
     oder
    Figure imgb0676
     bedeutet,
    Z8 -(C=O)-O-, -CH2-O-, -CF2-O- oder -CH2-CH2- bedeutet,
    o 0 oder 1 bedeutet,
    R91 und R92 unabhängig voneinander die vorstehend für R72 genannte Bedeutung besitzen,
    Figure imgb0677
     bedeutet,
    p und q unabhängig voneinander 0 oder 1 bedeuten.
  7. Medium nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es eine oder mehrere Verbindungen der Formel I
    Figure imgb0678
     enthält, worin
    Figure imgb0679
     oder
    Figure imgb0680
     bedeutet,
    Figure imgb0681
     oder
    Figure imgb0682
     bedeutet,
    n 0 oder 1 bedeutet,
    R11 und R12 unabhängig voneinander Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy, vorzugsweise mit 1 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclopropylen, 1,3-Cyclobutylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclopentylen ersetzt sein kann, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclopropylen, 1,3-Cyclobutylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclopentylen ersetzt sein kann, bedeuten, und R11 alternativ R1 bedeutet und R12 alternativ X1 bedeutet,
    R1 Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy, vorzugsweise mit 1 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclopropylen, 1,3-Cyclo-butylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclo-pentylen ersetzt sein kann, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclo-propylen, 1,3-Cyclobutylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclopentylen ersetzt sein kann, bedeutet, und
    X1 F, Cl, fluoriertes Alkyl, fluoriertes Alkenyl, fluoriertes Alkoxy oder fluoriertes Alkenyloxy bedeutet.
  8. Medium nach Anspruch 7, dadurch gekennzeichnet, dass die Gesamtkonzentration der Verbindungen der Formel T im gesamten Medium 1 % oder mehr bis 60 % oder weniger, vorzugsweise bis 30 % oder weniger beträgt.
  9. Medium nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es zusätzlich eine oder mehrere chirale Verbindungen enthält.
  10. Elektrooptische Anzeige oder elektrooptische Komponente, dadurch gekennzeichnet, dass sie ein flüssigkristallines Medium nach mindestens einem der Ansprüche 1 bis 9 enthält.
  11. Anzeige nach Anspruch 10, dadurch gekennzeichnet, dass sie auf dem IPS-, FFS-, HB-IPS- oder XB-FFS-Modus basiert.
  12. Anzeige nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass sie eine Aktivmatrix-Adressierungsvorrichtung enthält.
  13. Verwendung eines Mediums nach mindestens einem der Ansprüche 1 bis 9 in einer elektrooptischen Anzeige oder in einer elektrooptischen Komponente.
  14. Anzeige nach mindestens einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass es sich um eine mobile Anzeige handelt.
  15. Verfahren zur Herstellung eines flüssigkristallinen Mediums nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man eine oder mehrere Verbindungen der Formel T mit einer oder mehreren zusätzlichen mesogenen Verbindungen mischt.
  16. Verbindung der Formel T
    Figure imgb0683
     worin
    Figure imgb0684
     bedeutet,
    Figure imgb0685
     unabhängig voneinander
    Figure imgb0686
    Figure imgb0687
     bedeuten,
    bei denen die jeweiligen Ringe, und vorzugsweise die Phenylenringe, gegebenenfalls jeweils durch eine oder zwei Alkylgruppen, vorzugsweise durch Methyl- und/oder Ethylgruppen, vorzugsweise durch eine Methylgruppe substituiert sein können,
    n 1 oder 2 bedeutet,
    RS Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy, vorzugsweise mit 1 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclopropylen, 1,3-Cyclo-butylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclo-pentylen ersetzt sein kann, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen, bei denen eine Gruppe -CH2- durch Cyclo-propylen, 1,3-Cyclobutylen, 1,3-Cyclopentylen, 1,3-Cyclopentenylen, vorzugsweise durch Cyclopropylen oder 1,3-Cyclopentylen ersetzt sein kann, bedeutet, und
    XS ein fluoriertes Alkyl oder ein fluoriertes Alkoxy, vorzugsweise solche mit 1 bis 4 C-Atomen, stärker bevorzugt CF3 oder OCF3 bedeutet,
    und, wenn mindestens einer der vorhandenen Phenylringe eine Alkylgruppe trägt und/oder mindestens einer der vorhandenen Phenylringe zwei oder mehr F-Atome trägt und/oder n 2 ist und beide Phenylringe zwei oder mehr F-Atome tragen.
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DE10101022A1 (de) 2001-01-11 2002-07-18 Clariant Internat Ltd Muttenz Fluorierte Aromaten und ihre Verwendung in Flüssigkristallmischungen
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DE102010027099A1 (de) 2010-07-14 2012-01-19 Merck Patent Gmbh Flüssigkristallines Medium mit Stabilisator
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